Diatomaceous earth product and method for making product

ABSTRACT

A diatomaceous earth product may include diatomaceous earth having a loose weight density of less than about 14 lbs/ft3, and a stoichiometric ratio of alkali metal to iron and/or aluminum ranging from about 100% to about 400%. A diatomaceous earth product may include diatomaceous earth having a loose weight density of less than about 14 lbs/ft3, and a silica specific volume of at least about 3.2. A method for making a low loose weight density diatomaceous earth product may include providing a feed material comprising diatomaceous earth having a silica specific volume of at least about 3.5. The method may further include adding alkali flux to the feed material to achieve a combination having a stoichiometric ratio of alkali metal to iron and/or aluminum that ranges from about 100% to about 400%, calcining the combination at a temperature ranging from about 1,600° F. to about 2,200° F.

CLAIM FOR PRIORITY

This application is a divisional application of U.S. application Ser.No. 15/103,361, filed on Jun. 10, 2016, which is a U.S. national phaseentry under 35 U.S.C. § 371 from PCT International Application No.PCT/US2014/067873, filed Dec. 1, 2014, which claims the benefit ofpriority of U.S. Provisional Patent Application No. 61/914,196, filedDec. 10, 2013, to each of which this application claims the benefit ofpriority, and the entirety of the subject matter of each of which isincorporated herein by reference.

DESCRIPTION Field of the Disclosure

This disclosure relates to a biogenic silica product obtained fromdiatomaceous earth and methods for preparing biogenic silica products.More particularly, this disclosure relates to a biogenic silica product,which may bear the distinguishing porous and intricate structure ofsilica unique to diatomaceous earth and which may have a high silicacontent (i.e., silicon dioxide, SiO₂) and/or low loose weight density,resulting in a high silica specific volume (SSV). The present disclosurealso relates to modified, purified biogenic silica products that mayhave exceptionally low content of soluble metals and/or extremebrightness.

Background

The present disclosure relates to diatomaceous earth products, which mayboth retain the intricate and porous structure unique to diatomaceousearth (i.e., which have an intricate and porous diatomaceous silicastructure), and/or may have a unique combination of desirable physicaland chemical properties (such as, for example, high purity, low density,low soluble impurity content, low total impurity content, and/or highbrightness).

Diatomaceous earth products may be used in a wide variety ofapplications, including, but not limited to, separation, adsorption,support, and functional filler applications. At least some productsaccording to the present disclosure may exhibit the intricate and porousstructure unique to diatomite silica and/or exceptional purity, and maypermit greatly increased effectiveness in many of these applications.Diatomaceous earth products may be obtained from diatomaceous earth(also known as “kieselguhr”), which is a sediment enriched in biogenicsilica (i.e., silica produced or brought about by living organisms) inthe form of the siliceous frustules (i.e., shells or skeletons) ofdiatoms. Diatoms include a diverse array of microscopic, single-celled,golden brown algae of the class Bacillariophyceae, which possess anornate siliceous skeleton (i.e., a frustule) of varied and intricatestructure including two valves which, in the living diatom, fit togethermuch like parts of a pill box. The morphology of the frustules varieswidely among species and serves as the basis for taxonomicclassification; over 2,000 distinct species are known. The surface ofeach valve is characterized by a series of openings that include thecomplex fine structure of the frustule and impart a design that isdistinctive to individual species. The size of typical frustules rangesfrom 0.75 to 1,000 micrometers (microns), although the majority are inthe range of 10 to 150 microns. These frustules are sufficiently durableto retain much of their porous and intricate structure virtually intactthrough long periods of geologic time when preserved in certainconditions (e.g., conditions that maintain chemical equilibrium).

The fundamental chemical composition and the intricate and porousstructure of the diatom frustule may provide diatomaceous earth withunique commercial value and versatility unmatched by other natural formsof silica in certain applications; for example, filtration and fillerapplications. The fine particulate structure of the diatom skeletonimparts low density and high surface area, as well as high porosity andpermeability. Diatomaceous earth products may be processed ormanufactured by a variety of methods and from numerous resources,offering diversity in both physical and chemical characteristics.

For example, in the field of filtration, methods of particle separationfrom fluids may employ diatomaceous earth products as filter aids. Theintricate and porous structure unique to diatomite silica may beparticularly effective for the physical entrapment of particles infiltration processes. For example, diatomaceous earth products may beused to improve the clarity of fluids that contain suspended particlesor particulate matter, or that have turbidity.

Diatomaceous earth products may be applied to a septum to improveclarity and increase flow rate in filtration processes, for example, ina step sometimes referred to as “precoating.” Diatomaceous earthproducts may often be added directly to a fluid as it is being filteredto reduce the loading of undesirable particulate at the septum whilemaintaining a designed liquid flow rate, in a step often referred to as“body feeding.” Depending on the particular separation involved,diatomaceous earth products may be used in precoating and/or bodyfeeding.

In some filtration applications, different diatomaceous earth productsmay be blended together to further modify or improve the filtrationprocess. Also, diatomaceous earth products may sometimes be combinedwith other substances. In some cases, these combinations may involvesimple mixtures, for example, with cellulose, activated charcoal, clay,or other materials. In other cases, these combinations are composites inwhich diatomite products may be intimately compounded with otheringredients to make sheets, pads, or cartridges. Still more elaboratemodifications of any of some diatomaceous earth products may be used forfiltration or separation, involving, for example, surface treatment andthe addition of chemicals to diatomaceous earth products, mixtures, ortheir composites.

In certain circumstances, diatomaceous earth products may also exhibitunique adsorptive properties during filtration that may greatly enhanceclarification or purification of a fluid. These adsorptive propertiesmay be highly specific, and may depend on either weak forces forattraction of the adsorbed species to weak electrical charges at thesurface of diatomaceous earth, or on the reactivity of silanol (i.e.,≡Si—OH) functional groups that often occur at the diatomite surface. Forexample, an ionized silanol group (i.e., ≡Si—OH) may react with ahydronium ion (i.e., H₃O⁺) contributed by an acidic substance insolution, for example, citric acid (i.e., C₆H₈O₇), adsorbing the donatedH⁺ at the surface in the process.

The intricate and porous structure of silica unique to diatomaceousearth products may also permit their commercial use to provideanti-block properties to polymers. Diatomaceous earth products may oftenbe used to alter the appearance or properties of paints, enamels,lacquers, and related coatings and finishes. In addition to their use inpaper or cellulose-bearing filter media, diatomaceous earth products maybe used commercially in paper processing applications, and they may beessential to the processing of certain commercial catalysts.Diatomaceous earth products may also be used as chromatographicsupports, and may be particularly suited to, for example, gas-liquidchromatographic methods.

Regardless of the manner in which diatomaceous earth products are usedin separating particles from fluids, the diatomaceous earth productmakes contact with the fluid from which particles are being removed. Asingredients in polymers, plastics, paints, coatings, and/or otherformulations, diatomaceous earth products may also come into contactwith most of the other ingredients in the formulation. For this reason,high silica purity and low solubility of impurities in the diatomaceousearth product may be highly desirable properties. In addition, theefficiency and usefulness of a diatomaceous earth product used as afilter aid may also be related to its density when in contact with fluidduring filtration operations. In some instances, a diatomaceous earthproduct having a low density is highly desirable.

Highly purified diatomaceous earth products may be desirable fornumerous applications. As the effectiveness of diatomite in itsapplications may generally be related to the presence of the porous andintricate structure of silica unique to diatomite in combination withhigh silica purity, purified/processed diatomaceous earth products mayoffer distinguishing characteristics.

SUMMARY

In accordance with a first aspect, a diatomaceous earth product mayinclude diatomaceous earth having a loose weight density of less thanabout 14 pounds per cubic foot (lbs/ft³), and a stoichiometric ratio ofalkali metal to iron and/or aluminum ranging from about 100% to about400%. For example, the loose weight density may range from about 6lbs/ft³ to about 10 lbs/ft³, or from about 11 lbs/ft³ to about 14lbs/ft³ According to a further aspect the stoichiometric ratio of alkalimetal to iron and/or aluminum may range from about 125% to about 350%,from about 150% to about 300%, from about 150% to about 250%, from about175% to about 325%, from about 175% to about 300%, or from about 175% toabout 275%.

According to yet another aspect, the diatomaceous earth product may havea BET surface area ranging from about 0.5 square meter per gram (m²/g)to about 20 m²/g, from about 1 m²/g to about 20 m²/g, from about 1 m²/gto about 10 m²/g, from about 2 m²/g to about 10 m²/g, from about 1 m²/gto about 5 m²/g, or from about 3 m²/g to about 5 m²/g.

According to another aspect, particles of the diatomaceous earth productmay have a size ranging from about 20 US Mesh sieve to about 270 US Meshsieve. For example, particles of the diatomaceous earth product may havea size ranging from about 20 US Mesh sieve to about 200 US Mesh sieve,from about 60 US Mesh sieve to about 140 US Mesh sieve, or from about 80US Mesh sieve to about 120 US Mesh sieve. According to a further aspect,particles of the diatomaceous earth product may have a much narrowersize range for greater utility in any application. For example,particles of the diatomaceous earth product may have a size ranging fromabout 80 US Mesh sieve to about 100 US Mesh sieve.

According to a further aspect, the diatomaceous earth product may have asilica content of at least about 95% by weight. According to anotheraspect, the diatomaceous earth product may be one of non-calcined andnon-flux-calcined, and may have a silica content of at least about 95%by weight. According to a further aspect, the diatomaceous earth productmay have a silica content of at least about 90% by weight. According toanother aspect, the diatomaceous earth product may be flux-calcined, andmay have a silica content of at least about 90% by weight.

According to another aspect, the diatomaceous earth product may have asilica specific volume of at least about 3.2, at least about 3.5, atleast about 3.7, or at least about 4.

According to still another aspect, the diatomaceous earth product mayhave a content of at least 70% by weight, within two narrowly specifiedUS Mesh sieve sizes. According to a further aspect, the diatomaceousearth product may have a content of at least 80% by weight, within twonarrowly specified US Mesh sieve sizes. According to still a furtheraspect, the diatomaceous earth product may have a content of at least90% by weight, within two narrowly specified US Mesh sieve sizes. Forexample, the diatomaceous earth product may have a content of at least80% by weight, within 80 US Mesh (177 microns) and 100 US Mesh (149microns) sieve sizes, or the diatomaceous earth product may have acontent of at least 90% by weight, within 60 US Mesh (250 microns) and80 US Mesh (177 microns) sieve sizes.

According to a further aspect, the diatomaceous earth product may havean iron solubility ranging from about 0.5 parts per million to about 15parts per million. According to yet another aspect, the diatomaceousearth product may have a wet density less than about 16 lbs/ft³.

According to another aspect, the diatomaceous earth product may have anintricate and porous diatomaceous silica structure.

According to still another aspect, a diatomaceous earth product mayinclude a diatomaceous earth having a loose weight density of less thanabout 14 lbs/ft³, and a silica specific volume of at least about 3.2, atleast about 3.5, at least about 3.7, or at least about 4. According toanother aspect, the loose weight density may range from about 6 lbs/ft³to about 10 lbs/ft³, or from about 11 lbs/ft³ to about 14 lbs/ft³.

According to still a further aspect, the diatomaceous earth product mayhave a stoichiometric ratio of alkali metal to iron and/or aluminumranging from about 125% to about 350%. For example, the stoichiometricratio of alkali metal to iron and/or aluminum may range from about 150%to about 300%, from about 150% to about 250%, from about 175% to about325%, from about 175% to about 300%, or from about 175% to about 275%.

According to yet another aspect, the diatomaceous earth product may havea BET surface area ranging from about 0.5 m²/g to about 20 m²/g. Forexample, the diatomaceous earth product may have a BET surface arearanging from about 1 m²/g to about 20 m²/g, from about 1 m²/g to about10 m²/g, from about 2 m²/g to about 10 m²/g, from about 1 m²/g to about5 m²/g, or from about 3 m²/g to about 5 m²/g.

According to yet another aspect, particles of the diatomaceous earthproduct may have a size ranging from about 20 US Mesh sieve to about 270US Mesh sieve. For example, the particles of diatomaceous earth productmay have a size ranging from about 20 US Mesh sieve to about 200 US Meshsieve, from about 60 US Mesh sieve to about 140 US Mesh sieve, or fromabout 80 US Mesh sieve to about 120 US Mesh sieve.

According to a further aspect, the diatomaceous earth product may have asilica content of at least about 95% by weight. According to anotheraspect, the diatomaceous earth product may be one of non-calcined andnon-flux-calcined, and may have a silica content of at least about 95%by weight. According to a further aspect, the diatomaceous earth productmay have a silica content of at least about 90% by weight. According toanother aspect, the diatomaceous earth product may be flux-calcined, andmay have a silica content of at least about 90% by weight.

According to still a further aspect, a method for making a low looseweight density diatomaceous earth product may include providing a feedmaterial including diatomaceous earth having a silica specific volume ofat least about 3.2, at least about 3.5, at least about 3.7, or at leastabout 4. The method may further include adding alkali flux to the feedmaterial to achieve a combination having a stoichiometric ratio ofalkali metal to iron and/or aluminum ranging from about 100% to about400%. The method may also include calcining the combination at atemperature ranging from about 1,600° F. to about 2,200° F., whereinfollowing calcination, the diatomaceous earth product has a loose weightdensity of less than about 14 lbs/ft³. For example, the temperature mayrange from about 1,600° F. to about 2,150° F., or from about 1,600° F.to about 2,050° F.

According to a further aspect, the calcining may occur for a durationranging from about 15 minutes to about 60 minutes. For example, thecalcining may occur for a duration ranging from about 35 minutes toabout 45 minutes.

According to still another aspect, the alkali flux may be selected fromthe group consisting of sodium, potassium, and alkali or alkaline earthmetals.

According to another aspect, the loose weight density may range fromabout 6 lbs/ft³ to about 10 lbs/ft³. According to a further aspect, theloose weight density may range from about 11 lbs/ft³ to about 14lbs/ft³.

According to yet another aspect, the method may result in thestoichiometric ratio of alkali metal to iron and/or aluminum may rangefrom about 125% to about 350%. For example, the stoichiometric ratio ofalkali metal to iron and/or aluminum may range from about 150% to about300%, from about 150% to about 250%, from about 175% to about 325%, fromabout 175% to about 300%, or from about 175% to about 275%.

According to yet a further aspect, the method may result in thediatomaceous earth product having a BET surface area ranging from about0.5 m²/g to about 20 m²/g. For example, the diatomaceous earth productmay have a BET surface area ranging from about 1 m²/g to about 20 m²/g,from about 1 m²/g to about 10 m²/g, from about 2 m²/g to about 10 m²/g,from about 1 m²/g to about 5 m²/g, or from about 3 m²/g to about 5 m²/g.

According to another aspect, the method may result in particles of thediatomaceous earth product having a size ranging from about 20 US Meshsieve to about 270 US Mesh sieve. For example, the method may result inparticles of diatomaceous earth product having a size ranging from about20 US Mesh sieve to about 200 US Mesh sieve, from about 60 US Mesh sieveto about 140 US Mesh sieve, or from about 80 US Mesh sieve to about 120US Mesh sieve.

According to yet another aspect, the method may result in thediatomaceous earth product having a silica content of at least about 95%by weight. According to another aspect, the diatomaceous earth productmay be one of non-calcined and non-flux-calcined, and may have a silicacontent of at least about 95% by weight. According to a further aspect,the diatomaceous earth product may have a silica content of at leastabout 90% by weight. According to another aspect, the diatomaceous earthmay be flux-calcined, and may have a silica content of at least about90% by weight.

According to a further aspect, the method may result in the diatomaceousearth product having a silica specific volume of at least about 3.2. Forexample, the diatomaceous earth product may have a silica specificvolume of at least about 3.5, at least about 3.7, or at least about 4.

According to another aspect, the method may result in the diatomaceousearth product having a content of at least 70% by weight, within twonarrowly specified US Mesh sieve sizes. According to a further aspect,the method may result in the diatomaceous earth product having a contentof at least 80% by weight, within two narrowly specified US Mesh sievesizes. According to still another aspect, the method may result in thediatomaceous earth product having a content of at least 90% by weight,within two narrowly specified US Mesh sieve sizes. For example, themethod may result in the diatomaceous earth product having a content ofat least 80% by weight, within 80 US Mesh (177 microns) and 100 US Mesh(149 microns) sieve sizes, or the method may result in the diatomaceousearth product having a content of at least 90% by weight, within 60 USMesh (250 microns) and 80 US Mesh (177 microns) sieve sizes.

According to a further aspect, the method may result in the diatomaceousearth product having an iron solubility ranging from about 0.5 parts permillion to about 15 parts per million. According to yet another aspect,the method may result in the diatomaceous earth product having a wetdensity less than about 17 lbs/ft³. According to a further aspect, themethod may result in the diatomaceous earth product having a wet densityless than about 16 lbs/ft³. According to still another aspect, themethod may result in the diatomaceous earth product having a wet densityless than about 15 lbs/ft³.

According to a further aspect, the feed material may includediatomaceous earth having a silica specific volume of at least about3.5, or at least about 3.7. According to another aspect, the feedmaterial may include diatomaceous earth having a total silica content ormore than about 95% (w/w) SiO₂ on an ignited basis (e.g., in the rangeof about 95% to about 99.9% (w/w) SiO₂). According to some aspects, thefeed material may have a centrifuged wet density of less than about 0.28g/cm³ (e.g., in the range of about 0.15 g/cm³ to about 0.28 g/cm³).According to some aspects, the feed material may retain the intricateand porous structure unique to diatomite, and may have a permeabilitythat is typically less than 0.1 Darcy (e.g., in the range of about 0.001Darcy to about 0.1 Darcy). According to some aspects, the feed materialmay have a total iron content of less than 0.3% (w/w) Fe₂O₃ on anignited basis (e.g., in the range of about 0.005% to about 0.3% (w/w)Fe₂O₃), and a total aluminum content of less than 0.5% (w/w) Al₂O₃ on anignited basis (e.g., in the range of about 0.01% to about 0.5% (w/w)Al₂O₃) With respect to solubility, according to some aspects, the feedmaterial may have a specific resistance greater than 50 kQ-cm (e.g., inthe range of about 50 kQ-cm to about 250 kQ-cm), a beer-soluble ironcontent less than 7 mg Fe/kg feed (e.g., in the range of from about thequantitation limit to about 7 mg Fe/kg feed), and a beer-solublealuminum content less than 10 mg Al/kg feed (e.g., in the range of fromabout the quantitation limit to about 10 mg Al/kg feed).

According to yet another aspect, the method may result in thediatomaceous earth product having an intricate and porous diatomaceoussilica structure.

It is to be understood that both the foregoing general description andthe following detailed description are exemplary and explanatory onlyand are not restrictive of the invention, as claimed.

DESCRIPTION OF EXEMPLARY EMBODIMENTS

Reference will now be made in detail to exemplary embodiments.

According to some embodiments, a diatomaceous earth product may includediatomaceous earth having a loose weight density of less than about 14lbs/ft³, and a stoichiometric ratio of alkali metal to iron and/oraluminum ranging from about 100% to about 400%. For example, the looseweight density may range from about 6 lbs/ft³ to about 10 lbs/ft³, orfrom about 11 lbs/ft³ to about 14 lbs/ft³. According to a further aspectthe stoichiometric ratio of alkali metal to iron and/or aluminum mayrange from about 125% to about 350%, from about 150% to about 300%, fromabout 150% to about 250%, from about 175% to about 325%, from about 175%to about 300%, or from about 175% to about 275%.

One method for measuring loose weight density includes measuring theweight of a sample powder and the volume occupied by the sample powder,and dividing the former by the latter. For example, a scale (e.g., aMettler Digital Scale or equivalent) may be zeroed with respect to anempty calibrated container having a known volume (e.g., 625 cubiccentimeters (cc or cm³)). The sample powder is sifted through a screento break up any lumps and fluff the powder. The sifted powder isthereafter lifted with a scoop, and the powder is shaken into thecalibrated container with a rotary sifting motion until the container isoverflowing with the sifted powder. Excess powder is scraped off with astraight edge spatula. Thereafter, the powder-filled container isweighed, for example, to the nearest tenth of a gram. The loose weightdensity is determined using the following formula:Loose weight density (lbs/ft³)=Net weight (lbs)/volume (ft³).

According to some embodiments, the diatomaceous earth product may have aBET surface area ranging from about 0.5 m²/g to about 20 m²/g, fromabout 1 m²/g to about 20 m²/g, from about 1 m²/g to about 10 m²/g, fromabout 2 m²/g to about 10 m²/g, from about 1 m²/g to about 5 m²/g, orfrom about 3 m²/g to about 5 m²/g.

One technique for calculating specific surface area (or BET surfacearea) of physical adsorption molecules is with the Brunauer, Emmett, andTeller (“BET”) theory. The application of BET theory to a particularadsorbent component yields a measure of the material's specific surfacearea, known as “BET surface area.” As used herein, “surface area” refersto BET surface area.

According to some embodiments, particles of the diatomaceous earthproduct may have a size ranging from about 20 US Mesh sieve to about 200US Mesh sieve. For example, particles of the diatomaceous earth productmay have a size ranging from about 60 US Mesh sieve to about 140 US Meshsieve, or from about 80 US Mesh sieve to about 120 US Mesh sieve.

According to some embodiments, the diatomaceous earth product may have asilica content of at least about 95% by weight. According to someembodiments, the diatomaceous earth product may be one of non-calcinedand non-flux-calcined, and may have a silica content of at least about95% by weight. According to some embodiments, the diatomaceous earthproduct may have a silica content of at least about 90% by weight.According to some embodiments, the diatomaceous earth product may beflux-calcined, and may have a silica content of at least about 90% byweight.

For some embodiments, the diatomaceous earth products may convenientlybe described as “non-calcined,” “calcined,” or “flux-calcined,”depending on how the product is prepared. These broad classes reflectthe method of preparation employed, which may determine the permeabilityof the product, for example, by moderating the degree to whichagglomeration and sintering occurs, which may be of general importanceto the useful application of the diatomaceous earth products.

As used herein, the term “non-calcined” with respect to a product refersto a product that has not been subjected to calcination orflux-calcination. As used herein, the term “calcined” with respect to aproduct refers to a product that has been subjected to calcination. Asused herein, the term “flux-calcined” with respect to a product refersto a product that has been subjected to flux-calcination (i.e.,calcination in the presence of a flux).

While the silica of diatomaceous earth is predominantly of an amorphoustype that resembles mineral opal, crystalline quartz dust or sand issometimes present which, although composed of silica, does not emulatethe intricate and porous structure associated with diatomaceous earth ordiatomite products. Upon calcination or flux-calcination, products maybe formed in which diatomaceous earth particles are sintered to oneanother into larger agglomerated masses, thus modifying some of theproperties of the diatomite products. Even after intense calcining, somediatomite products retain much of their intricate and porous structure,although conversion of amorphous hydrated silica to amorphous anhydroussilica, cryptocrystalline cristobalite, and/or cryptocrystalline quartzmay result from such processing.

Accurate measurements of total silica content may be determined by usingx-ray fluorescence spectrometry. This example technique may also beuseful to determine the total content of other elements, such as, forexample, aluminum, iron, and sodium.

For example, in a “fused tetraborate matrix” x-ray fluorescence methodused to determine the total element contents of embodiments of thediatomaceous earth products, a 2 gram diatomite sample (after roastingat 950° C. in air for one hour), is fused with 7.7 grams of lithiumtetraborate (i.e., Li₂B₄O₇), and the melt is cast into a 40 millimeterbutton. The button is analyzed on a Philips PW1600 simultaneous x-rayfluorescence spectrometer. This system may be calibrated using referencematerials, most of which are tabulated. Counting time on major elements,such as, for example, silicon, aluminum, iron, or sodium, is 60 seconds,and each element is determined through its own fixed channel. Loss onignition data are obtained from the roasting. To accommodate the naturalloss of hydration within the silica structure, the total silicon,aluminum, iron, and sodium contents for all examples are reported on anignited basis for their respective high oxides (i.e., SiO₂, Al₂O₃,Fe₂O₃, and Na₂O). As used herein, the term “on an ignited basis”reflects the pre-treatment of the sample by roasting at 950° C. in airfor one hour prior to analysis.

In an alternative “pressed binder matrix” x-ray fluorescence method fordetermining total element content, a 3 gram diatomite sample (afterroasting at 950° C. in air for one hour) is added to 0.75 gram ofSPECTROBLEND® (Chemplex) binder. The mixture is milled by shaking for 5minutes in a tungsten carbide mixing vial with an impact ball. Theresulting mixture is then pressed in a 31 millimeter die to 24,000pounds per square inch (165 MPa) to form a pellet. Chemical compositionmay thereafter be determined using a Spectrace 6000 energy-dispersivex-ray fluorescence spectrometer operating under fundamental parameters,with calibration using six diatomite standards prepared in the samemanner as the samples being tested. The instrument employs anelectronically-cooled Li(Si) detector and 50 kV rhodium target x-raysource, and is configured to result in sample excitation withapproximately 50% deadtime. Peak intensities from spectra are analyzedby lineshape analysis comparison with single element reference spectra.Specifically, the K_(alpha) peak intensities used for silicon, aluminum,and iron determinations correspond with energies of 1.740 keV, 1.487keV, and 6.403 keV, respectively. The peak intensities for the diatomitestandards are thereafter converted into pure element count rates, whichare used for determining element contents in samples, by peak intensityand data fitting. This method achieves results that are comparable tothe aforementioned method for all elements except sodium, for which therelative error is significantly greater than for the fused tetraboratematrix method.

According to some embodiments, the diatomaceous earth product may have asilica specific volume of at least about 3.2. For example, thediatomaceous earth product may have a silica specific volume of at leastabout 3.5, at least about 3.7, or at least about 4.

Under some circumstances, it may be desirable for a diatomite product tohave both a high total silica content and a low centrifuged wet density.This combination of properties may provide a measure of the usefulnessof the product as compared to diatomite products of lesser purity.Impure diatomite is expected to have greater centrifuged wet densityowing to the occupation of its porous, intricate structure with theimpure substances. One measure to quantify this combination ofproperties, the specific volume occupied by silica, may be defined as:Silica Specific Volume (SSV)=Fraction Silica Content/Centrifuged WetDensity,

where the fraction silica content is calculated by dividing the percentby weight of SiO₂ on an ignited basis by 100, and the centrifuged wetdensity is expressed in units of grams per cubic centimeter (g/cm³). Forexample, for a sample with a measured total silica content of 99.1%(w/w) SiO₂ and a centrifuged wet density of 0.27 g/cm³, a silicaspecific volume (SSV) of 0.991/0.27, equal to about 3.7, is obtained Asis readily apparent from the equation, the greater the silica specificvolume, the greater the diatomite purity of the product.

The influence of both the content of total silica and wet density may beaccounted for in this expression, silica specific volume (SSV). Evensmall changes in the total silica content or the centrifuged wet densityresult in significant changes of the silica specific volume, and thesilica specific volume therefore may provide a highly discriminatingmeasure of diatomite product purity.

According to some embodiments, the diatomaceous earth product may have acontent of at least 70% by weight, within two narrowly specified US Meshsieve sizes, According to some embodiments, the diatomaceous earthproduct may have a content of at least 80% by weight, within twonarrowly specified US Mesh sieve sizes. According to some embodiments,the diatomaceous earth product may have a content of at least 90% byweight, within two narrowly specified US Mesh sieve sizes. For example,the diatomaceous earth product may have a content of at least 80% byweight, within 80 US Mesh (177 microns) and 100 US Mesh (149 microns)sieve sizes. According to some embodiments, the diatomaceous earthproduct may have a content of at least 90% by weight, within 60 US Mesh(250 microns) and 80 US Mesh (177 microns) sieve sizes.

An example method for determining the minimum weight percent passing orretained on a specific sieve opening on an Alpine tester follows: A.Select the appropriate two sieves for material to be tested; B. Weighout a 10 gram sample on scale; C. Pour the sample on the smaller openingsieve, place it on an Alpine tester, and cover it with the Lucite lid;D. Adjust vacuum to ½″ above the neutral level (the water level when thevacuum is off) on the graduated scale of the water manometer (“U” shapedtube); E. Set timer for 2 minutes; F. Remove sieve after 2 minutes,brush sample from screen (smaller openings) into cup, weigh, and notethis as weight “A” for Step 1 that follows; and G. Transfer the sampleonto the second sieve (larger openings), cover with Lucite lid, andfollow same procedures D, E, and F above, but note this as weight “D”for Step 2 that follows. Following performance of procedures A-G, thefollowing calculations are performed:

The percent retained on each sieve or mesh fraction is calculated:

-   -   Step 1: From Smaller Sieve:        (10.0−A)×10=B        -   Where:            -   A=weight of residue            -   B=% of undersized material    -   Step 2: From Larger Sieve:        D×10=C        -   Where:            -   D=weight of residue            -   C=% of oversized material    -   Step 3:        (100−B C)=E        -   Where:            -   B=% of undersized material            -   C=% of oversized material            -   E=% mesh fraction.

According to a further aspect, the diatomaceous earth product may havean iron solubility ranging from about 0.5 parts per million to about 15parts per million.

An example method for determining the iron solubility follows: Weigh 5.0g of sample into a tared 250 ml Erlenmeyer flask. Add 25 ml of 3.0N HCl.Manually swirl for 5 seconds every 5 minutes for 15 minutes. Add 50 mlDI water and swirl for 2 minutes. Filter this through a #42 Whatmanfilter using a Buchner funnel and vacuum flask. Pour another 50 ml DIwater on the filter cake and filter to dryness. Pour some of this into asample holder. Load the samples and run them on the Inductively CoupledPlasma (ICP) Optical Emission Spectrophotometer for analysis. Thisinstrument compares the intensity of the specific frequency of lightemitted from the Iron (Fe) in the sample to that of standard referencematerials of known Iron (Fe) concentration for the determination ofcontent in the extract. This concentration is used to calculate thesoluble Iron (Fe) content in milligrams per kilogram in the original drysample.

According to some embodiments, the diatomaceous earth products may havea blue light reflected brightness of at least about 80%.

In many instances, especially in filler applications, diatomite productshave greater utility if they have a high reflected brightness. Anexample of a method for determining reflected brightness involvesmeasuring the amount of blue light reflected from a smooth surface ofthe product, as determined using a special instrument that provides asource of illumination, a blue filter, and a detector (PhotovoltBrightness Meter, Model 575), The instrument is calibrated usingstandard plates of known reflectance in blue light, after the lamp hasbeen turned on, and its emission output has stabilized. If the sample tobe tested is a non-calcined product, the sample should be dried toconstant weight at 110° C. in air, and subsequently allowed to cool toroom temperature in air (i.e., dried). If the sample to be tested is acalcined or flux-calcined product, the sample should be dried toconstant weight at room temperature in air. A plastic plate having adepression machined into it is slightly overfilled with the sample,which is then compressed with a smooth-faced plate using a circularpressing motion. The smooth-faced plate is carefully removed with asliding motion to insure an even, unmarred surface. The sample is thenplaced at the instrument's sample port with the blue filter in place.The reflectance measurement is then read directly from the instrument.Blue light reflectance can also be calculated from measurements ofbrightness obtained using other instruments, for example, thoseavailable from Hunter or CIE (Commission Internationale de l'Eclairage).

According to some embodiments, the non-calcined diatomaceous earthproducts have centrifuged wet densities of less than about 18 lbs/ft³.For example, according to some embodiments, the non-calcineddiatomaceous earth products have a wet density ranging from about 1lb/ft³ to about 18 lbs/ft³, from about 5 lbs/ft³ to about 18 lbs/ft³,from about 7 lbs/ft³ to about 18 lbs/ft³, or from about 9 lbs/ft³ toabout 18 lbs/ft³. According to some embodiments, the calcineddiatomaceous earth products have centrifuged wet densities of less thanabout 18 lbs/ft³. For example, according to some embodiments, thecalcined diatomaceous earth products have a wet density ranging fromabout 1/ft³ to about 18 lbs/ft³, from about 6 lbs/ft³ to about 18lbs/ft³, from about 6 lbs/ft³ to about 16 lbs/ft³, from about 6 lbs/ft³to about 15 lbs/ft³, or from about 6 lbs/ft³ to about 14 lbs/ft³.According to some embodiments, the flux-calcined diatomaceous earthproducts have centrifuged wet densities of less than about 19 lbs/ft³.For example, according to some embodiments, the flux-calcineddiatomaceous earth products have a wet density ranging from about 1lb/ft³ to about 19 lbs/ft³, from about 6 lbs/ft³ to about 19 lbs/ft³,from about 6 lbs/ft³ to about 16 lbs/ft³, from about 6 lbs/ft³ to about15 lbs/ft³, or from about 6 lbs/ft³ to about 14 lbs/ft³.

An indicator of degree to which a diatomite product retains the porousand intricate structure unique to diatomite may be obtained by measuringits centrifuged wet density or settled wet density, or an equivalentmeasure of its packed density, since the magnitude of the density islimited by the packing arrangement that can be achieved. Wet densitymagnitude may be critical because it may reflect the void volumeavailable to entrain particulate matter in a filtration process, and itmay be one of the most important criteria to determine the filtrationefficiency. Diatomite products with lower wet densities have greatervoid volumes, and thus, generally greater filtration efficiency.

Convenient measurements of packed densities of diatomite powders aregenerally more reproducible in liquid media than in gases. One preferredmethod for determining the packed density of some embodiments of thediatomaceous products is by measurement of the centrifuged wet density.If the sample to be tested is a non-calcined product, the sample shouldbe dried to constant weight at 110° C. in air, and subsequently allowedto cool to room temperature in air (i.e., dried). If the sample to betested is a calcined or flux-calcined product, the sample should bedried to constant weight at room temperature in air. A sample of knownweight between 0.50 grams and 2.00 grams is placed in a calibratedcentrifuge tube, to which deionized water is added to fill up about halfthe volume of the tube. The mixture is shaken thoroughly until all ofthe sample is wetted, and there is no dry powder remaining. Additionaldeionized water is added to, for example, just below the 15 mL level ofthe centrifuge tube to rinse down any mixture adhering to the side ofthe tube from shaking. Thereafter, the tube is centrifuged (e.g., via aBeckman AccuSpin) for three minutes or more at 2,500 rpm or more.Following centrifugation, the tube is carefully removed so as not todisturb the solids, and the level (i.e., volume) of the settled matteris measured to the nearest half of a 0.1 mL graduation on the tube. Thecentrifuged wet density of the known weight of powder is readilycalculated by dividing the sample weight by the measured volume, forexample, using the following formula:Wet density (g/cm³)=((100−A)×wt)/(B×100)=Wet density (lbs/ft³)/62.4,

where A equals percent moisture; wt equals weight in grams; and B equalstube volume reading.

Typically, centrifuged wet density is reported in units of pounds percubic foot (lbs/ft³) or in units of grams per cubic centimeter (g/cm³);the conversion factor for these units is 1 lb/ft³ is equal to about0.01602 g/cm³.

According to still another aspect, a diatomaceous earth product mayinclude a diatomaceous earth having a loose weight density of less thanabout 14 lbs/ft3, and a silica specific volume of at least about 3.2.For example, the diatomaceous earth product may have a silica specificvolume of at least about 3.5, at least about 3.7, or at least about 4.According to another aspect, the loose weight density may range fromabout 6 lbs/ft3 to about 10 lbs/ft3, or from about 11 lbs/ft3 to about14 lbs/ft3.

According to some embodiments, the feed material may includediatomaceous earth having a silica specific volume of at least about 3.5or, for example, at least about 3.7. According to some embodiments, thefeed material may include diatomaceous earth having a total silicacontent or more than about 95% (w/w) SiO₂ on an ignited basis (e.g., inthe range of about 95% to about 99.9% (w/w) SiO₂). According to someembodiments, the feed material may have a centrifuged wet density ofless than about 0.28 g/cm³ (e.g., in the range of about 0.15 g/cm³ toabout 0.28 g/cm³). According to some embodiments, the feed material mayretain the intricate and porous structure unique to diatomite, and mayhave a permeability that is typically less than 0.1 Darcy (e.g., in therange of about 0.001 Darcy to about 0.1 Darcy). According to someembodiments, the feed material may have a total iron content of lessthan 0.3% (w/w) Fe₂O₃ on an ignited basis (e.g., in the range of about0.005% to about 0.3% (w/w) Fe₂O₃), and a total aluminum content of lessthan 0.5% (w/w) Al₂O₃ on an ignited basis (e.g., in the range of about0.01% to about 0.5% (w/w) Al₂O₃). With respect to solubility, accordingto some embodiments, the feed material may have a specific resistancegreater than 50 kQ-cm (e.g., in the range of about 50 kQ-cm to about 250kQ-cm), a beer-soluble iron content less than 7 mg Fe/kg feed (e.g., inthe range of from about the quantitation limit to about 7 mg Fe/kgfeed), and a beer-soluble aluminum content less than 10 mg Al/kg feed(e.g., in the range of from about the quantitation limit to about 10 mgAl/kg feed).

The method may further include adding alkali flux to the feed materialto achieve a combination having a stoichiometric ratio of alkali metalto iron and/or aluminum ranging from about 100% to about 400%. Themethod may also include calcining the combination at a temperatureranging from about 1,600° F. to about 2,200° F., wherein followingcalcination, the diatomaceous earth product has a loose weight densityof less than about 14 lbs/ft3. For example, the temperature may rangefrom about 1,600° F. to about 2,150° F., or from about 1,600° F. toabout 2,050° F.

According to some embodiments, the calcining may occur for a durationranging from about 15 minutes to about 60 minutes. For example, thecalcining may occur for a duration ranging from about 35 minutes toabout 45 minutes.

According to some embodiments, the alkali flux may be selected from thegroup consisting of sodium, potassium, and any other alkali or alkalineearth metals. For example, the alkali flux may include soda ash (sodiumcarbonate).

According to some embodiments of the methods, the resulting loose weightdensity may range from about 6 lbs/ft³ to about 10 lbs/ft³. According tosome embodiments, the resulting loose weight density may range fromabout 11 lbs/ft³ to about 14 lbs/ft³.

According to some embodiments of the methods, the method may result inthe stoichiometric ratio of alkali metal to iron and/or aluminum mayrange from about 125% to about 350%. For example, the stoichiometricratio of alkali metal to iron and/or aluminum may range from about 150%to about 300%, from about 150% to about 250%, from about 175% to about325%, from about 175% to about 300%, or from about 175% to about 275%.

According to some embodiments of the methods, the method may result inthe diatomaceous earth product having a BET surface area ranging fromabout 0.5 m²/g to about 20 m²/g. For example, the diatomaceous earthproduct may have a BET surface area ranging from about 1 m²/g to about20 m²/g, from about 1 m²/g to about 10 m²/g, from about 2 m²/g to about10 m²/g, from about 1 m²/g to about 5 m²/g, or from about 3 m²/g toabout 5 m²/g.

According to some embodiments of the methods, the method may result inparticles of the diatomaceous earth product having a size ranging fromabout 20 US Mesh sieve to about 270 US Mesh sieve. For example,particles of the diatomaceous earth product may have a size ranging fromabout 20 US Mesh sieve to about 200 US Mesh sieve, from about 60 US Meshsieve to about 140 US Mesh sieve, or from about 80 US Mesh sieve toabout 120 US Mesh sieve.

According to some embodiments of the methods, the method may result inthe diatomaceous earth product having a silica content of at least about95% by weight. According to some embodiments, the resulting diatomaceousearth product may be one of non-calcined and non-flux-calcined, and mayhave a silica content of at least about 95% by weight. According to someembodiments of the methods, the resulting diatomaceous earth product mayhave a silica content of at least about 90% by weight. According to someembodiments of the methods, the resulting diatomaceous earth may beflux-calcined, and may have a silica content of at least about 90% byweight.

According to some embodiments of the methods, the method may result inthe diatomaceous earth product having a silica specific volume of atleast about 3.2. For example, the diatomaceous earth product may have asilica specific volume of at least about 3.5, at least about 3.7, or atleast about 4.

According to some embodiments of the methods, the method may result inthe diatomaceous earth product having a content of at least 70% byweight, within two narrowly specified US Mesh sieve sizes. According tosome embodiments, the method may result in the diatomaceous earthproduct having a content of at least 80% by weight, within two narrowlyspecified US Mesh sieve sizes. According to some embodiments, the methodmay result in the diatomaceous earth product having a content of atleast 90% by weight, within two narrowly specified US Mesh sieve sizes.For example, the method may result in the diatomaceous earth producthaving a content of at least 80% by weight, within BO US Mesh (177microns) and 100 US Mesh (149 microns) sieve sizes, or the method mayresult in the diatomaceous earth product having a content of at least90% by weight, within 60 US Mesh (250 microns) and 80 US Mesh (177microns) sieve sizes.

According to some embodiments of the methods, the method may result inthe diatomaceous earth product having an iron solubility ranging fromabout 0.5 parts per million to about 15 parts per million.

An exemplary feed material for producing the diatomaceous earth productsaccording to some embodiments included a crude ore of diatomaceous earththat was crushed and hammer-milled to pass through a 12 mesh screen(i.e., with openings of approximately 1.82 mm), slurried with water to apulp density of 20 to 23% solids, and then attrition-milled to passthrough a screen with openings of approximately 174 microns. The slurrywas diluted to 8 to 10% solids with water, and introduced to a 1 inch(2.5 cm) hydrocyclone operated at a pressure of 50 to 60 pounds persquare inch (psi) (345 to 414 kPa). The overflow fraction containedparticles with a median particle size of 10 to 12 microns. A collectorwas prepared by dissolving equal volumes of tripentylamine (i.e.N(C₅H₁₁)₃) in acetic acid (i.e., CH₃COOH) prior to addition. In apreconditioning step, the pH of the diatomite overflow was adjusted towithin a desired range of pH 3 to 5 using sulfuric acid (i.e., H₂SO₄),and sufficient tripentylamine solution was added to deliver 360 to 390grams of tripentylamine per 1000 kg of solids. Mechanical flotation wasthen effected in two stages, a rougher stage and a scavenger stage. Thediatomite flotation product from the second scavenger stage wasrecirculated in combination with hydrocyclone overflow teed to the firstrougher stage flotation, with a sufficient quantity of tripentylaminesolution delivered directly to the flotation cells to add a 240 to 260gram supplement of tripentylamine per 1000 kg of solids. The overallflotation process was adjusted to provide a 60 to 65% yield of flotationproduct. The flotation product was then thickened to a pulp density of10% solids using 600 grams of SuperFloc 127 Plus (Cytec, apolyacrylamide (i.e., [CH—CH(CONH₂)]_(n)) flocculent) per 1,000 kg ofsolids, then leached for two hours with 2 N sulfuric acid (i.e., H₂SO₄)maintained at a temperature of 90 to 95° C. The slurry was dewateredwith a pressure filter, the cake rinsed with deionized water to obtain aminimum rinse water specific resistance of 250 κΩ-cm, and then dried toconstant weight at 110° C. in air in an oven.

Upon ultimate analysis, this exemplary non-calcined feed material wasfound to have a total silica content of 99.1% (w/w) SiO₂, found on anignited basis, as determined by x-ray fluorescence using thefused-tetraborate matrix method. The feed material further had a totalaluminum content of 0.31% (w/w) reported as Al₂O₃, and a total ironcontent of 0.15% (w/w) reported as Fe₂O₃, as determined by x-rayfluorescence using the fused-tetraborate matrix method. Its centrifugedwet density was 0.27 g/cm³. From this information, the silica specificvolume SSV for this feed material was 3.7.

According to some embodiments, the purified diatomaceous earth productsmay have extraordinarily high silica content. In addition to a highsilica content, these exemplary products may also retain the intricateand porous structure that is characteristic of diatomaceous earth (i.e.,these products have an intricate and porous diatomaceous silicastructure), which may be desirable in many applications for thediatomaceous earth product to be effective. This unique combination ofproperties may result in, for example, a desirable low centrifuged wetdensity, which may further result in a high silica specific volume.

According to some embodiments, the diatomaceous earth products may havea low density in conjunction with low impurity solubility, which maypermit for increased capacity, flow, clarity, and/or occupancy per unitof weight in spatially-limited applications, while significantlyreducing the contribution of undesirable aluminum, iron, and/or otherelements from the diatomaceous earth product to a contacted material.

According to some embodiments, the purified diatomaceous earth productsand their further modifications may be useful in the processing,treatment, and/or formulation of other materials. For example, infiltration applications, the diatomaceous earth products and theirfurther modifications may be applied to a septum to improve clarity andincrease flow rate in filtration processes, and/or added directly to afluid as it is being filtered to reduce the loading of undesirableparticulate at the septum. The products may be used in conjunction withother media during filtration, for example, cellulose, activatedcharcoal, clay, or other materials. The products may also be used inpreparing composites, being intimately compounded with other ingredientsto make sheets, pads, and/or cartridges. The appropriate selection ofwhich modification of the purified diatomaceous earth products may bedetermined according to the specific application. For example, in afiltration process desiring exceptional clarity but tolerates slowerflow rate, a purified diatomaceous earth product of the non-calcined orcalcined classes may be preferred. Alternatively, in a filtrationprocess desiring high flow rate but does not require exceptionalclarity, a purified diatomaceous earth product of the flux-calcinedclass may be preferred. Similar reasoning applies to use of the purifieddiatomaceous earth products when used in conjunction with othermaterials, and/or when preparing composite materials containing theproduct. The quantity of product used may be similarly determinedaccording to the specific process to which it is applied.

Use of the purified diatomaceous earth products according to someembodiments as functional fillers, for example, in paints and coatings,or in polymers, may be accomplished by direct addition into theformulation at a particular concentration to achieve the desired effect.Both the flatting property of the products in paints and coatings, aswell as the anti-block property of the products in polymers, may bederived from the irregular surface provided by the porous, intricatestructure of at least some embodiments of the diatomaceous earthproducts.

According to some embodiments, silanized hydrophobic or hydrophilicdiatomaceous earth products may be desirable when these propertiesfurther improve the filtration or functional filler performance, owingto their greater compatibility with other materials or Ingredients in aspecific application. The alteration of surface characteristics throughsilanization may be especially desirable for chromatographicapplications, as these characteristics may strongly influence theeffectiveness of chromatographic separations for specific systems. Forexample, hydrophobic surfaces on a chromatographic support reducesurface activity of the support and reduce tailing to a considerabledegree when used for the analytical determination of many organiccompounds, such as pesticides.

According to some embodiments, the diatomaceous earth products may alsobe desirable for further organic derivatizations, such as, for example,the coupling of a protein to an aminosilanized support. For example,protein A, a polypeptide derived from a bacterial source, has beencoupled to an aminosilanized diatomite-based support for use in clinicaltreatment of immunologic disorders.

Other embodiments of the invention will be apparent to those skilled inthe art from consideration of the specification and practice of theinvention disclosed herein. It is intended that the description andexamples be considered as exemplary only, with a true scope and spiritof the invention being indicated by the following claims,

What is claimed is:
 1. A diatomaceous earth product, the productcomprising diatomaceous earth having a loose weight density that rangesfrom about 11 lbs/ft³ to about 14 lbs/ft³, and a silica specific volumeof at least about 3.2.
 2. The product of claim 1, wherein thediatomaceous earth product has a silica specific volume of at leastabout 3.5.
 3. The product of claim 1, wherein the diatomaceous earthproduct has a silica specific volume of at least about
 4. 4. The productof claim 1, wherein the diatomaceous earth product has a stoichiometricratio of alkali metal to iron and/or aluminum ranging from about 125% toabout 350%.
 5. The product of claim 1, wherein the diatomaceous earthproduct has a stoichiometric ratio of alkali metal to iron and/oraluminum ranging from about 150% to about 300%.
 6. The product of claim1, wherein the diatomaceous earth product has a stoichiometric ratio ofalkali metal to iron and/or aluminum ranging from about 175% to about325%.
 7. The product of claim 1, wherein the diatomaceous earth producthas a BET surface area ranging from about 0.5 m²/g to about 20 m²/g. 8.The product of claim 1, wherein the diatomaceous earth product has a BETsurface area ranging from about 1 m²/g to about 10 m²/g.
 9. The productof claim 1, wherein the diatomaceous earth product has a BET surfacearea ranging from about 1 m²/g to about 5 m²/g.
 10. The product of claim1, wherein particles of the diatomaceous earth product have a sizeranging from about 20 US Mesh sieve to about 200 US Mesh sieve.
 11. Theproduct of claim 1, wherein the diatomaceous earth product has a silicacontent of at least about 95% by weight.
 12. The product of claim 11,wherein the diatomaceous earth product is one of non-calcined andnon-flux-calcined.
 13. The product of claim 1, wherein the diatomaceousearth product has a silica content of at least about 90% by weight. 14.The product of claim 13, wherein the diatomaceous earth product isflux-calcined.
 15. The product of claim 1, wherein the diatomaceousearth product has a content of at least 70% by weight, within 120 USMesh (125 microns) and 140 US Mesh (105 microns) sieve sizes.
 16. Theproduct of claim 1, wherein the diatomaceous earth product has an ironsolubility ranging from about 0.5 parts per million to about 15 partsper million.
 17. The product of claim 1, wherein the diatomaceous earthproduct has a wet density less than about 16 lbs/ft³.
 18. The product ofclaim 1, wherein the diatomaceous earth product has an intricate andporous diatomaceous silica structure.